WO2015046316A1 - Hydrogenation catalyst for heavy hydrocarbon oil and hydrogenation method for heavy hydrocarbon oil - Google Patents
Hydrogenation catalyst for heavy hydrocarbon oil and hydrogenation method for heavy hydrocarbon oil Download PDFInfo
- Publication number
- WO2015046316A1 WO2015046316A1 PCT/JP2014/075402 JP2014075402W WO2015046316A1 WO 2015046316 A1 WO2015046316 A1 WO 2015046316A1 JP 2014075402 W JP2014075402 W JP 2014075402W WO 2015046316 A1 WO2015046316 A1 WO 2015046316A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heavy hydrocarbon
- hydrocarbon oil
- oil
- catalyst
- zinc
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 56
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 56
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 38
- 239000011701 zinc Substances 0.000 claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000737 periodic effect Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 abstract description 26
- 238000006477 desulfuration reaction Methods 0.000 abstract description 23
- 230000023556 desulfurization Effects 0.000 abstract description 23
- 238000003860 storage Methods 0.000 abstract description 10
- 239000003921 oil Substances 0.000 description 85
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 24
- 229910052717 sulfur Inorganic materials 0.000 description 21
- 239000011593 sulfur Substances 0.000 description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000013049 sediment Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- -1 asphaltene Chemical compound 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007324 demetalation reaction Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8873—Zinc, cadmium or mercury
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- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
Definitions
- the present invention relates to a hydrotreating catalyst for heavy hydrocarbon oil and a method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst.
- a hydrotreating catalyst suitable for improving the storage stability of hydrotreated oil obtained by hydrotreating heavy hydrocarbon oil containing heavy metals such as sulfur, asphaltene, nickel and vanadium.
- a hydrotreating method suitable for demetalizing heavy hydrocarbon oil in the upstream part of the catalyst bed using the hydrotreating catalyst.
- a hydrotreating catalyst in which an active metal is supported on an inorganic oxide support containing alumina and zinc, thereby improving the average pore diameter of the catalyst without reducing the strength of the catalyst ( For example, see Patent Document 1.)
- hydrotreated heavy hydrocarbon oil is heated and stored in order to maintain fluidity in consideration of workability at the time of shipment until it is shipped. Moreover, after being shipped as a product, it may be stored for a long time until it is used. For this reason, depending on the thermal history and the atmosphere at the time of storage, sediment may occur during storage, which may cause clogging of the filter, damage to the pump, and the like.
- the present invention uses a hydrotreating catalyst capable of improving the storage stability of a hydrotreated heavy hydrocarbon oil without reducing desulfurization activity or demetalization activity, and the hydrotreating catalyst. It is an object of the present invention to provide a method for hydrotreating heavy hydrocarbon oil.
- the inventors of the present invention as a result of hydrogenation treatment of heavy hydrocarbon oil, a hydrogenation active component on a zinc-containing alumina support containing a specific amount of zinc particles of a specific size.
- the present inventors have found that a hydrotreated oil with a reduced amount of latent sediment can be obtained by using a hydrotreating catalyst that supports bismuth.
- the present invention relates to the following heavy hydrocarbon oil hydrotreating catalyst and heavy hydrocarbon oil hydrotreating method.
- At least one Group 6 metal of the periodic table is supported on a zinc-containing alumina support containing 1 to 15% by mass of zinc oxide particles having an average particle diameter of 2 to 12 ⁇ m based on the support.
- the hydrotreating catalyst according to the present invention uses a zinc-containing alumina support containing a specific amount of zinc and has a large average pore diameter and specific surface area, and therefore has excellent desulfurization activity and demetalization activity.
- the zinc-containing alumina support carries zinc oxide particles of a specific size, a heavy hydrocarbon oil that is difficult to generate sediment is obtained by hydrotreating using the hydrotreating catalyst. be able to.
- zinc-containing alumina containing 1 to 15% by mass, preferably 2 to 12% by mass of zinc in terms of oxide based on the carrier is used as the carrier.
- the strength of the carrier can be increased by adding zinc to the alumina carrier.
- support basis, in terms of oxide means that the mass of all elements contained in the support is calculated as each oxide, and the ratio of the oxide mass to the total mass Means.
- the oxide mass of zinc is determined in terms of zinc oxide.
- the zinc-containing alumina support in the hydrotreating catalyst according to the present invention contains zinc oxide particles having an average particle size of 2 to 12 ⁇ m, preferably 4 to 10 ⁇ m, more preferably 5 to 9 ⁇ m. If the average particle diameter of the zinc oxide particles contained in the support is 12 ⁇ m or less, sufficient interaction with alumina is obtained, and a heavy hydrocarbon oil after hydrotreatment having sufficient storage stability can be obtained. On the other hand, when the average particle diameter of the zinc oxide particles contained in the carrier is 2 ⁇ m or more, zinc and alumina are easily mixed during the production of the phosphorus / zinc-containing alumina carrier.
- the particle size of the zinc oxide particle was measured by the laser diffraction scattering method based on JISR1629, and the volume average of particle size distribution was made into the average particle diameter.
- the zinc oxide particles to be contained in the zinc-containing alumina support preferably have a purity of 99% or more.
- Group 6 metal In the hydrotreating catalyst according to the present invention, at least one Group 6 metal of the periodic table (hereinafter sometimes referred to as “Group 6 metal”) is supported on the zinc-containing alumina support.
- the Group 6 metal include Mo (molybdenum) and W (tungsten). Mo is particularly preferable.
- the Group 6 metal may be present in the form of a simple metal or in the form of a metal compound such as a metal sulfide. Group 6 metals may be used alone or in combination of two or more.
- the hydrotreating catalyst according to the present invention may carry another hydrogenation active metal as the second metal component.
- Other hydrogenation active metals as the second metal component include Group 8-10 metals of the periodic table such as Ni (nickel), Co (cobalt), Fe (iron) (hereinafter referred to as “Group 8-10 metals”). Is preferred).
- the hydrogenation active metal supported as the second metal component may be used alone or in combination of two or more.
- Specific combinations of metal components supported by the zinc-containing alumina support in the hydrotreating catalyst according to the present invention include various combinations such as Mo—Ni, Mo—Co, and W—Ni. The combination of is preferable.
- “Group 6 metal of the periodic table” means a Group 6 metal in the long-period type periodic table
- “Group 8-10 metal of the periodic table” means in the long-period type periodic table. Means a Group 8-10 metal.
- the amount of the Group 6 metal supported on the zinc-containing alumina support is not particularly limited. However, when it is not used in combination with the second metal component (hereinafter referred to as “single use”), 2 to 15 mass in terms of support and oxide. %, Preferably 4 to 12% by mass. When used in combination with the second metal component (hereinafter referred to as combined use), 2 to 15% by mass, preferably 5 to 10% by mass in terms of oxide, based on the carrier. It is.
- the amount of the other hydrogenation active metal supported as the second metal component may be appropriately selected. However, in the amount of the Group 6 metal supported, 0.001 to 5% by mass in terms of catalyst and oxide, preferably Is 1 to 4% by mass. Increasing the supported amount of the second metal component increases the hydrotreating activity, particularly the demetalization activity, but the catalyst life tends to be shortened. Tends to be difficult to obtain.
- the average pore diameter of the hydrotreating catalyst according to the present invention is 18 to 35 nm, preferably 18 to 30 nm, more preferably 20 to 30 nm. If the average pore diameter is 18 nm or more, sufficient metal removal activity is obtained, and if it is 35 nm or less, sufficient hydrogenation activity is obtained.
- the specific surface area of the hydrotreating catalyst according to the present invention is 70 to 150 m 2 / g, preferably 90 to 140 m 2 / g.
- the specific surface area is 70 m 2 / g or more, sufficient hydrotreating activity is obtained, and when it is 150 m 2 / g or less, a preferable average pore diameter is obtained, and thus sufficient metal removal activity is obtained.
- a method for preparing the hydrotreating catalyst according to the present invention a method comprising the following steps may be mentioned. First, an aqueous solution containing an alumina raw material is gelled, and the resulting gel is heated and aged, and then an alumina gel is obtained by performing an acidic aqueous solution treatment, washing and removing impurities, and adjusting water content. Next, zinc oxide particles are mixed with the alumina gel. Next, a zinc-containing alumina carrier is prepared by treating this mixture by a usual treatment method such as molding, drying, and firing. A hydrotreating catalyst is prepared by supporting a Group 6 metal on this zinc-containing alumina support and further supporting another active metal as required.
- alumina raw material any material containing aluminum can be used, but aluminum salts such as aluminum sulfate and aluminum nitrate are preferred. These alumina raw materials are usually provided as an aqueous solution, and the concentration thereof is not particularly limited, but is preferably 2 to 50% by mass, more preferably 5 to 40% by mass.
- an aqueous solution containing an alumina raw material is neutralized with a base such as ammonia, a neutralizing agent such as aluminate or sodium aluminate, or a precipitant such as hexamethylenetetramine or calcium carbonate.
- a base such as ammonia
- a neutralizing agent such as aluminate or sodium aluminate
- a precipitant such as hexamethylenetetramine or calcium carbonate.
- the amount of the neutralizing agent used is not particularly limited, but is preferably 30 to 70% by mass with respect to the total amount of the aqueous solution containing the alumina raw material and the neutralizing agent.
- the amount of the precipitant used is not particularly limited, but is preferably 30 to 70% by mass with respect to the total amount of the aqueous solution containing the alumina raw material and the precipitant.
- a hydrotreating catalyst having a desired average pore diameter pH, temperature, etc. when gelling with a neutralizing agent or a precipitating agent may be adjusted.
- the average pore diameter of the hydrotreating catalyst is adjusted to a desired value within the range of the present invention by appropriately adjusting the pH in the range of 4 to 8 and the temperature in the range of 30 to 90 ° C. Can be.
- a catalyst having a large average pore diameter can be obtained by increasing the pH to the alkali side during gel formation.
- the average pore diameter can also be adjusted by heat aging of the alumina gel.
- the aging time is preferably 5 hours or more. The longer the time, the larger the average pore diameter and the sharper the pore distribution.
- the aging temperature is preferably 80 to 95 ° C. The higher the temperature, the shorter the aging time can be, but if the aging temperature is too high, the alumina gel may be altered.
- the pH during aging is preferably 9-12. When the pH is 9 or more, ripening proceeds rapidly, and when the pH is 12 or less, there is little risk of alteration of alumina.
- the alumina gel after heat aging is treated with an acidic aqueous solution as described above.
- Nitric acid, hydrochloric acid, sulfuric acid and the like can be used as the acidic aqueous solution, and nitric acid is preferable.
- the acidic aqueous solution has a pH of 1 to 5.5, preferably a pH of 2 to 4. If the pH is 1 or more, the crystal structure of alumina is not easily destroyed even by an acid, and if the pH is 5.5 or less, it does not take time to stop ripening.
- a preferred embodiment of the acidic aqueous solution treatment is an embodiment in which a nitric acid aqueous solution is added to alumina gel, adjusted to pH 2 to 3, and sufficiently stirred at a temperature of 15 to 60 ° C. to complete ripening.
- aqueous alkaline solution is added to the alumina gel that has been treated with an acidic aqueous solution to adjust the pH to 9 to 13, preferably 10 to 12.
- an aqueous ammonia solution is preferable.
- the pH-adjusted alumina gel is filtered or dried to adjust the water content.
- the moisture adjustment is performed by adding water as well as filtration or drying.
- the moisture adjustment is performed to facilitate the molding of the catalyst.
- the water content after moisture adjustment is preferably 60 to 95% by mass.
- the fine surface structure of alumina can be controlled by adjusting the temperature and method during drying for moisture adjustment.
- the drying temperature for adjusting the moisture content of the alumina gel is preferably less than 100 ° C., and in particular, a method of preparing by drying by sufficient filtration without applying heat as much as possible is preferable. . Thereby, the metal removal performance can be increased.
- the zinc oxide particles are mixed with the moisture-adjusted alumina gel so as to be 1 to 15% by mass in terms of zinc oxide based on the finished carrier. Thereafter, a mixture of the obtained alumina gel and zinc oxide particles is molded. Molding can be performed by various molding methods such as extrusion molding and pressure molding.
- Molded zinc-containing alumina carrier is dried and fired.
- the drying temperature at this time is preferably 15 to 150 ° C., particularly preferably 100 to 120 ° C., and the drying time is preferably 2 hours or more, particularly preferably 3 to 11 hours.
- the firing temperature is preferably 600 ° C. or more, particularly preferably 700 to 900 ° C., and the firing time is preferably 30 minutes or more, particularly preferably 1 to 4 hours.
- the method for supporting the group 6 metal or other hydrogenation active metal as the second metal component on the zinc-containing alumina support prepared as described above may be a known method such as an impregnation method or a coprecipitation method.
- the zinc-containing alumina support contains a hydrogenation-active metal component as in the method of precipitating the hydrogenation-active metal component in a state where the zinc-containing alumina support is immersed in a solution containing these hydrogenation-active metal components. It is possible to employ a method in which a hydrogenation active metal is supported on a zinc-containing alumina support by contacting with the solution to be prepared. When a plurality of hydrogenation active metals are supported, the plurality of hydrogenation active metals may be supported at a time, or may be supported one after another regardless of the order.
- the hydrotreating catalyst according to the present invention can be obtained by drying and calcining the zinc-containing alumina support carrying the hydrogenation-active metal.
- the drying temperature and drying time at this time are preferably 15 to 150 ° C., particularly preferably 100 to 120 ° C., and the drying time is 2 like the drying temperature and drying time of the zinc-containing alumina carrier. More than the time is preferable, and 3 to 12 hours is particularly preferable.
- the firing temperature is preferably 350 to 800 ° C., particularly preferably 400 to 700 ° C., and the firing time is preferably 1 hour or more, particularly preferably 3 to 12 hours.
- the catalyst shape of the hydrotreating catalyst according to the present invention is not particularly limited, and can be various shapes used for ordinary catalyst shapes.
- the shape of the hydrotreating catalyst according to the present invention is preferably a three-leaf type or a four-leaf type.
- the catalyst diameter may be about 1.1 to 2.5 mm.
- the hydrotreating catalyst according to the present invention may be used by mixing with a known catalyst or a known inorganic oxide support.
- the hydrotreating catalyst according to the present invention is preferably presulfided before being used for hydrotreating heavy hydrocarbon oil.
- the preliminary sulfidation method a method in which a hydrocarbon oil or gas phase sulfide containing 1% by mass or more of sulfur is passed over the catalyst under high temperature and high pressure is used. By performing this preliminary sulfidation, most of the hydrogenation active metal component becomes a sulfide. In addition, a part or all of the hydrogenation active metal component may become a sulfide also depending on the sulfur content of the heavy hydrocarbon oil during the hydrotreatment.
- the hydrotreating catalyst according to the present invention described in detail above is a catalyst suitable for effectively removing heavy metals from heavy hydrocarbon oils containing heavy metals such as sulfur, asphaltene, nickel and vanadium. It is. That is, the hydrotreating catalyst according to the present invention is a catalyst suitable for producing a middle distillate or a low sulfur heavy oil as a product as it is from a heavy hydrocarbon oil. Therefore, the hydrotreating catalyst according to the present invention can be suitably used particularly as a demetallation catalyst, for example, in the front stage of the catalyst bed when heavy hydrocarbon oil is hydrotreated in multiple stages.
- the heavy hydrocarbon oil hydrotreating method of the present invention is carried out using the hydrotreating catalyst according to the present invention.
- a method for producing middle distillate or a low-sulfur heavy oil as a product from heavy hydrocarbon oil, or a demetallizing method for the front part of the catalyst bed in a multistage hydroprocessing method for heavy hydrocarbon oil is preferred.
- Heavy hydrocarbon oils used in the hydrotreating method according to the present invention include atmospheric distillation residue oil obtained by distillation from crude oil, vacuum distillation residue oil, bisbreaking oil that is pyrolysis oil, other than petroleum Examples thereof include tar sand oil, shale oil, and the like, which are heavy hydrocarbon oils, and mixtures thereof.
- Preferred are atmospheric distillation residue oil, vacuum distillation residue oil, and mixed oil thereof.
- the heavy hydrocarbon oil is subjected to hydrotreatment process according to the present invention, density of 0.91 ⁇ 1.10g / cm 3, in particular 0.95 ⁇ 1.05g / cm 3, sulfur content 2 to 6% by mass, particularly 2 to 5% by mass, metal content of nickel, vanadium, etc. is 1 to 1500 ppm, particularly 20 to 400 ppm, and asphaltene content is 2 to 15% by mass, especially 3 to 10% by mass.
- Some heavy hydrocarbon oils are preferred.
- the hydrogenation treatment of heavy hydrocarbon oil in the present invention refers to treatment by contact of heavy hydrocarbon oil and hydrogen, hydrorefining with relatively low severity of reaction conditions, and slightly high degree of severity. This includes hydrorefining, hydroisomerization, hydrodealkylation, demetalization, and other heavy hydrocarbon oil reactions in the presence of hydrogen, especially for low-sulfur heavy oils such as middle distillates.
- a demetallation reaction at the front stage of the catalyst bed in the production reaction and the heavy hydrocarbon oil multistage hydrotreating method is preferred. For example, it includes residual oil from atmospheric distillation, hydrodesulfurization, hydrodenitrogenation, hydrocracking of distillate and residual oil from vacuum distillation, and hydrorefining of wax and lubricating oil fractions.
- the hydrotreating conditions in the hydrotreating method according to the present invention are a temperature of 300 to 420 ° C., preferably 350 to 410 ° C., and a pressure (hydrogen partial pressure) of 3 to 20 MPa, preferably 8 to 19 MPa.
- LHSV liquid hourly space velocity
- the catalytic activity particularly the demetalization activity is sufficiently exhibited. If temperature is 420 degrees C or less, since thermal decomposition of heavy hydrocarbon oil does not advance too much, catalyst deterioration is suppressed. If the hydrogen partial pressure is 3 MPa or more, the hydrogenation reaction is likely to proceed, and if it is 20 MPa or less, the demetalization activity is moderately improved and the catalyst life is prolonged. When the hydrogen / oil ratio is 400 m 3 / m 3 or more, the hydrogenation activity is improved, and when it is 3000 m 3 / m 3 or less, the economy is excellent. Liquid hourly space velocity is excellent in economical efficiency in 0.1 h -1 or more, catalytic activity is improved if 3h -1 or less.
- the hydrotreating catalyst according to the present invention is used as a fixed bed, moving bed or fluidized bed in an appropriate reactor and treated in the reactor. Introduce heavy heavy hydrocarbon oil.
- the hydrotreating catalyst according to the present invention is maintained as a fixed bed so that heavy hydrocarbon oil passes downward through the fixed bed.
- the hydrotreating catalyst according to the present invention may be used in a single reactor or may be used in several consecutive reactors, and it is particularly preferable to use a multistage reactor.
- the hydrotreating catalyst according to the present invention is suitable for pretreatment demetallization of heavy hydrocarbon oil as described above.
- Table 1 shows the average particle diameter of the zinc oxide particles used in Examples and Comparative Examples.
- the particle size of the zinc oxide particles was measured by a laser diffraction scattering method according to JIS R1629, and the volume average particle size distribution was defined as the average particle size.
- Example 1 Preparation of hydrotreating catalyst A After heating 10 kg of 5 mass% aqueous sodium aluminate solution to 60 ° C, 2.8 kg of 25 mass% aqueous aluminum sulfate solution was slowly added, and finally the pH of the solution was adjusted. It was set to 7. At this time, the temperature of the solution was kept at 60 ° C. The alumina slurry produced
- the aqueous dispersion of the gel was heated to 90 ° C. and aged for 40 hours while stirring and refluxing. Thereafter, a 5N aqueous nitric acid solution was added to the aqueous dispersion of the gel to adjust the pH to 2, followed by stirring for 15 minutes. Furthermore, 10 mass% ammonia aqueous solution was added and it adjusted to pH11. The obtained gel aqueous dispersion was filtered, and then water was adjusted at 25 ° C. so that the viscosity was easy to mold. The water content of the alumina gel after moisture adjustment was 70% by mass.
- zinc oxide 1 as zinc oxide particles was added to the alumina gel so as to be 7.8% by mass based on the carrier, and mixed well with a kneader until sufficiently uniform.
- the obtained zinc-containing alumina gel was extrusion molded, dried at 110 ° C. for 10 hours, and calcined at 800 ° C. for 2 hours.
- 100 g of the calcined zinc-containing alumina support was impregnated with a solution prepared by dissolving ammonium paramolybdate and nickel nitrate in 100 g of water so that the amount of Mo was 9% by mass and that of Ni was 2% by mass in terms of oxides.
- the impregnated zinc-containing alumina support was heated and dried at 110 ° C. for 4 hours and calcined at 550 ° C. for 3 hours to prepare a hydrotreating catalyst A.
- the zinc content of the hydrotreating catalyst A was 7.8% by mass in terms of support and oxide, the hydrogenation active metal content was 9% by mass and Mo was 2% by mass in terms of catalyst and oxide. It was.
- the shape of the hydrotreating catalyst A was a four-leaf type, and the diameter was 1.3 mm.
- Example 2 Preparation of hydrotreating catalyst B A hydrotreating catalyst B was prepared in the same manner as in Example 1 except that zinc oxide 1 was replaced with zinc oxide 2.
- hydrotreating catalyst b was prepared in the same manner as in Example 1 except that zinc oxide 1 was replaced with zinc oxide 4.
- the average pore diameter is an average value of D calculated as a function of P.
- the hydrotreating catalyst was charged into a high-pressure flow reactor to form a fixed bed catalyst layer, and pretreated under the following conditions.
- a mixed fluid of the raw material oil heated to the reaction temperature and the hydrogen-containing gas is introduced from the upper part of the reaction apparatus, and a desulfurization reaction and a hydrogenation reaction that is a decomposition reaction proceed under the following conditions to generate A mixed fluid of oil and gas was allowed to flow out from the lower part of the reactor, and the produced oil was separated by a gas-liquid separator.
- the measurement method is JIS K 2249-1 “Crude oil and petroleum products-Density test method and density / mass / capacity conversion table (vibration density test method)”, and the sulfur content is JIS K 2541-4 “Crude oil and Petroleum products-Sulfur content test method Part 4: Radiation-type excitation method ", latent sediment content conformed to JPI-5S-60-2000. Specifically, the potential sediment content was analyzed by the following method.
- the contents of nickel and vanadium were in accordance with the Japan Petroleum Institute Standard JPI-5S-62-2000 “Petroleum Products Metal Analysis Test Method (ICP Luminescence Analysis Method)”.
- the asphaltene content was filtered through a cellulose filter after toluene was added to the sample, and the toluene-insoluble content was recovered. This insoluble content was defined as asphaltene content.
- Toluene was added to the sample, and the resin was filtered through a cellulose filter, and the toluene-soluble component as a filtrate was concentrated.
- a heptane solution obtained by adding heptane to this concentrate was passed through an activated alumina packed column and separated into saturated, aromatic and resin components, and the resin component was recovered.
- Catalyst pretreatment conditions The preliminary sulfidation of the catalyst was carried out with a vacuum gas oil at a hydrogen partial pressure of 10.3 MPa and 370 ° C. for 12 hours. Then, it switched to the raw material oil for activity evaluation.
- Reaction conditions Reaction temperature: 385 ° C. Pressure (hydrogen partial pressure); 10.3 MPa, Liquid space velocity; 0.4 h ⁇ 1 , Hydrogen / oil ratio: 1690 m 3 / m 3 .
- Raw oil properties Oil type: Vacuum distillation residue of Middle Eastern crude oil, Density (15 ° C.); 1.037 g / cm 3 ; Sulfur component; 4.27% by mass; Vanadium; 91 ppm, Nickel; 54 ppm, Asphaltene content: 7.8% by mass.
- the catalytic activity was analyzed by the following method.
- the reactor was operated at 385 ° C., and the product oil 20 days after the start of operation was collected and its properties (desulfurization rate (HDS) (%), desulfurization reaction rate constant (Ks), desulfurization specific activity (%), demetalization rate, (HDM)) was analyzed.
- the results are shown in Table 3.
- Desulfurization reaction rate constant (Ks) The desulfurization reaction rate constant (Ks) is a constant in the reaction rate equation for obtaining the second order reaction order with respect to the reduction amount of the sulfur content (Sp) of the product oil. It calculated by the following formula
- Sf sulfur content (mass%) in the raw material oil
- Sp Sulfur content (% by mass) in the product oil
- LHSV Liquid space velocity (h -1 ).
- the amount of resin is larger when the catalyst A or the catalyst B is used than when the catalyst a or the catalyst b is used. There were obviously few. That is, the product oil obtained by using the catalyst A or the catalyst B was less likely to generate sediment than the oil obtained by using the catalyst a or the catalyst b, and was excellent in storage stability. From these results, heavy hydrocarbons hydrotreated without reducing the desulfurization activity of the hydrotreating catalyst by using a hydrotreating catalyst using a support containing zinc oxide particles having specific physical properties. It is clear that the content of latent sediment in the oil can be lowered and the storage stability can be improved.
- hydrotreating catalyst of the present invention According to the hydrotreating catalyst of the present invention and the heavy hydrocarbon oil using the hydrotreating catalyst, storage of the hydrotreated heavy hydrocarbon oil without reducing the desulfurization activity or the demetallization activity. Stability can be improved.
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Abstract
Description
本願は、2013年9月27日に、日本に出願された特願2013-201799号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a hydrotreating catalyst for heavy hydrocarbon oil and a method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst. Particularly, a hydrotreating catalyst suitable for improving the storage stability of hydrotreated oil obtained by hydrotreating heavy hydrocarbon oil containing heavy metals such as sulfur, asphaltene, nickel and vanadium. And a hydrotreating method suitable for demetalizing heavy hydrocarbon oil in the upstream part of the catalyst bed using the hydrotreating catalyst.
This application claims priority on September 27, 2013 based on Japanese Patent Application No. 2013-201799 filed in Japan, the contents of which are incorporated herein by reference.
[1] 平均粒子径が2~12μmの酸化亜鉛粒子を担体基準で1~15質量%含有する亜鉛含有アルミナ担体に、少なくとも1種の周期表第6族金属が担持されており、平均細孔径が18~35nmであり、比表面積が70~150m2/gであることを特徴とする、重質炭化水素油の水素化処理触媒。
[2] 前記[1]の水素化処理触媒の存在下、温度300~420℃、圧力3~20MPa、水素/油比400~3000m3/m3、及び液空間速度0.1~3h-1の条件で、重質炭化水素油の接触反応を行うことを特徴とする、重質炭化水素油の水素化処理方法。 That is, the present invention relates to the following heavy hydrocarbon oil hydrotreating catalyst and heavy hydrocarbon oil hydrotreating method.
[1] At least one Group 6 metal of the periodic table is supported on a zinc-containing alumina support containing 1 to 15% by mass of zinc oxide particles having an average particle diameter of 2 to 12 μm based on the support. Is a heavy hydrocarbon oil hydrotreating catalyst characterized by having a specific surface area of 70 to 150 m 2 / g.
[2] In the presence of the hydrotreating catalyst of [1], a temperature of 300 to 420 ° C., a pressure of 3 to 20 MPa, a hydrogen / oil ratio of 400 to 3000 m 3 / m 3 , and a liquid space velocity of 0.1 to 3 h −1. A method for hydrotreating heavy hydrocarbon oil, wherein the catalytic reaction of heavy hydrocarbon oil is carried out under the conditions of:
なお、本発明及び本願明細書において、「担体基準、酸化物換算で」とは、担体中に含まれる全ての元素の質量をそれぞれの酸化物として算出し、その合計質量に対する酸化物質量の割合を意味する。亜鉛の酸化物質量は酸化亜鉛に換算して求める。 In the hydrotreating catalyst according to the present invention, zinc-containing alumina containing 1 to 15% by mass, preferably 2 to 12% by mass of zinc in terms of oxide based on the carrier is used as the carrier. In general, the larger the average pore diameter of the catalyst, the lower the strength of the catalyst. However, the strength of the carrier can be increased by adding zinc to the alumina carrier. By setting the content of zinc oxide particles in the zinc-containing alumina support within the above range, both the average pore diameter and the specific surface area can be sufficiently increased without excessively reducing the catalyst strength.
In the present invention and the specification of the present application, “support basis, in terms of oxide” means that the mass of all elements contained in the support is calculated as each oxide, and the ratio of the oxide mass to the total mass Means. The oxide mass of zinc is determined in terms of zinc oxide.
担体に含有させる酸化亜鉛粒子の平均粒子径が12μm以下であれば、アルミナとの相互作用が十分得られ、十分な貯蔵安定性がある水素化処理後の重質炭化水素油が得られる。一方で、担体に含有させる酸化亜鉛粒子の平均粒子径が2μm以上であると、リン・亜鉛含有アルミナ担体の製造時において亜鉛とアルミナが混合し易い。 The zinc-containing alumina support in the hydrotreating catalyst according to the present invention contains zinc oxide particles having an average particle size of 2 to 12 μm, preferably 4 to 10 μm, more preferably 5 to 9 μm.
If the average particle diameter of the zinc oxide particles contained in the support is 12 μm or less, sufficient interaction with alumina is obtained, and a heavy hydrocarbon oil after hydrotreatment having sufficient storage stability can be obtained. On the other hand, when the average particle diameter of the zinc oxide particles contained in the carrier is 2 μm or more, zinc and alumina are easily mixed during the production of the phosphorus / zinc-containing alumina carrier.
なお、本発明において、「周期表第6族金属」とは、長周期型周期表における第6族金属を意味し、「周期表第8~10族金属」とは、長周期型周期表における第8~10族金属を意味する。 The hydrotreating catalyst according to the present invention may carry another hydrogenation active metal as the second metal component. Other hydrogenation active metals as the second metal component include Group 8-10 metals of the periodic table such as Ni (nickel), Co (cobalt), Fe (iron) (hereinafter referred to as “Group 8-10 metals”). Is preferred). The hydrogenation active metal supported as the second metal component may be used alone or in combination of two or more. Specific combinations of metal components supported by the zinc-containing alumina support in the hydrotreating catalyst according to the present invention include various combinations such as Mo—Ni, Mo—Co, and W—Ni. The combination of is preferable.
In the present invention, “Group 6 metal of the periodic table” means a Group 6 metal in the long-period type periodic table, and “Group 8-10 metal of the periodic table” means in the long-period type periodic table. Means a Group 8-10 metal.
第二金属成分の担持量を増加させると、水素化処理活性、特に脱金属活性は増加するが、触媒寿命は短くなる傾向があり、減少させると、十分な水素化処理活性、特に脱金属活性が得られ難くなる傾向がある。 The amount of the Group 6 metal supported on the zinc-containing alumina support is not particularly limited. However, when it is not used in combination with the second metal component (hereinafter referred to as “single use”), 2 to 15 mass in terms of support and oxide. %, Preferably 4 to 12% by mass. When used in combination with the second metal component (hereinafter referred to as combined use), 2 to 15% by mass, preferably 5 to 10% by mass in terms of oxide, based on the carrier. It is. The amount of the other hydrogenation active metal supported as the second metal component may be appropriately selected. However, in the amount of the Group 6 metal supported, 0.001 to 5% by mass in terms of catalyst and oxide, preferably Is 1 to 4% by mass.
Increasing the supported amount of the second metal component increases the hydrotreating activity, particularly the demetalization activity, but the catalyst life tends to be shortened. Tends to be difficult to obtain.
先ず、アルミナの原料を含む水溶液をゲル化し、生成したゲルを加熱熟成し、酸性水溶液処理、不純物の洗浄除去、水分調整を行うことによりアルミナゲルを得る。次いで、このアルミナゲルに酸化亜鉛粒子を混合する。次に、この混合物を、成型、乾燥、焼成等の通常の処理法で処理することにより、亜鉛含有アルミナ担体を調製する。この亜鉛含有アルミナ担体に、第6族金属を担持し、更に必要に応じて他の活性金属を担持することにより、水素化処理触媒を調製する。 As a suitable method for preparing the hydrotreating catalyst according to the present invention, a method comprising the following steps may be mentioned.
First, an aqueous solution containing an alumina raw material is gelled, and the resulting gel is heated and aged, and then an alumina gel is obtained by performing an acidic aqueous solution treatment, washing and removing impurities, and adjusting water content. Next, zinc oxide particles are mixed with the alumina gel. Next, a zinc-containing alumina carrier is prepared by treating this mixture by a usual treatment method such as molding, drying, and firing. A hydrotreating catalyst is prepared by supporting a Group 6 metal on this zinc-containing alumina support and further supporting another active metal as required.
本発明に係る水素化処理触媒を実際のプロセスに用いる際には、公知の触媒又は公知の無機質酸化物担体と混合して用いてもよい。 The catalyst shape of the hydrotreating catalyst according to the present invention is not particularly limited, and can be various shapes used for ordinary catalyst shapes. The shape of the hydrotreating catalyst according to the present invention is preferably a three-leaf type or a four-leaf type. The catalyst diameter may be about 1.1 to 2.5 mm.
When the hydrotreating catalyst according to the present invention is used in an actual process, it may be used by mixing with a known catalyst or a known inorganic oxide support.
常圧蒸留残渣油と減圧蒸留残渣油とを混合する場合は、その性状にもよるが、混合割合としては、減圧蒸留残渣油が1~60容量%程度となるように混合することが多い。 Heavy hydrocarbon oils used in the hydrotreating method according to the present invention include atmospheric distillation residue oil obtained by distillation from crude oil, vacuum distillation residue oil, bisbreaking oil that is pyrolysis oil, other than petroleum Examples thereof include tar sand oil, shale oil, and the like, which are heavy hydrocarbon oils, and mixtures thereof. Preferred are atmospheric distillation residue oil, vacuum distillation residue oil, and mixed oil thereof.
When mixing the atmospheric distillation residue oil and the vacuum distillation residue oil, depending on the properties, the mixing ratio is often such that the vacuum distillation residue oil is about 1 to 60% by volume.
水素分圧が3MPa以上ならば、水素化反応が進行し易く、20MPa以下ならば適度に脱金属活性が向上し触媒寿命が長くなる。
水素/油比が400m3/m3以上では水素化活性が改善され、3000m3/m3以下であれば、経済性に優れる。
液空間速度が0.1h-1以上では経済性に優れ、3h-1以下ならば触媒活性が改善される。 When the temperature is 300 ° C. or higher, the catalytic activity, particularly the demetalization activity is sufficiently exhibited. If temperature is 420 degrees C or less, since thermal decomposition of heavy hydrocarbon oil does not advance too much, catalyst deterioration is suppressed.
If the hydrogen partial pressure is 3 MPa or more, the hydrogenation reaction is likely to proceed, and if it is 20 MPa or less, the demetalization activity is moderately improved and the catalyst life is prolonged.
When the hydrogen / oil ratio is 400 m 3 / m 3 or more, the hydrogenation activity is improved, and when it is 3000 m 3 / m 3 or less, the economy is excellent.
Liquid hourly space velocity is excellent in economical efficiency in 0.1 h -1 or more, catalytic activity is improved if 3h -1 or less.
5質量%のアルミン酸ナトリウム水溶液10kgを60℃に加熱した後、25質量%の硫酸アルミニウム水溶液2.8kgをゆっくり加え、最終的に溶液のpHを7とした。この時、当該溶液の温度は60℃を保持した。以上の操作により生成したアルミナスラリーを濾過し、濾別されたアルミナゲルを0.3質量%のアンモニア水溶液で繰り返し洗浄した。
次いで、洗浄後のアルミナゲルに水5kgを加え、更に10質量%のアンモニア水溶液を加えて、当該ゲルの水分散液をpH11に調整した。次に、当該ゲルの水分散液を90℃に加熱し、撹拌、還流しながら40時間熟成した。
その後、当該ゲルの水分散液に5Nの硝酸水溶液を加えてpH2に調整し、15分間撹拌した。更に、10質量%のアンモニア水溶液を加えてpH11に調整した。得られたゲルの水分散液を濾過した後、25℃で加水して成型し易い粘度になるように水分調整を行った。水分調整後のアルミナゲルの水含有量は、70質量%であった。 [Example 1] Preparation of hydrotreating catalyst A After heating 10 kg of 5 mass% aqueous sodium aluminate solution to 60 ° C, 2.8 kg of 25 mass% aqueous aluminum sulfate solution was slowly added, and finally the pH of the solution was adjusted. It was set to 7. At this time, the temperature of the solution was kept at 60 ° C. The alumina slurry produced | generated by the above operation was filtered, and the alumina gel separated by filtration was repeatedly wash | cleaned with 0.3 mass% ammonia aqueous solution.
Next, 5 kg of water was added to the washed alumina gel, and a 10% by mass aqueous ammonia solution was further added to adjust the aqueous dispersion of the gel to pH 11. Next, the aqueous dispersion of the gel was heated to 90 ° C. and aged for 40 hours while stirring and refluxing.
Thereafter, a 5N aqueous nitric acid solution was added to the aqueous dispersion of the gel to adjust the pH to 2, followed by stirring for 15 minutes. Furthermore, 10 mass% ammonia aqueous solution was added and it adjusted to pH11. The obtained gel aqueous dispersion was filtered, and then water was adjusted at 25 ° C. so that the viscosity was easy to mold. The water content of the alumina gel after moisture adjustment was 70% by mass.
焼成された亜鉛含有アルミナ担体100gを、パラモリブデン酸アンモニウムと硝酸ニッケルとを各々酸化物換算でMo9質量%、Ni2質量%となるように100gの水に溶解させた液に、含浸した。含浸後の亜鉛含有アルミナ担体を110℃で4時間加熱乾燥し、550℃で3時間焼成して、水素化処理触媒Aを調製した。 Subsequently, zinc oxide 1 as zinc oxide particles was added to the alumina gel so as to be 7.8% by mass based on the carrier, and mixed well with a kneader until sufficiently uniform. The obtained zinc-containing alumina gel was extrusion molded, dried at 110 ° C. for 10 hours, and calcined at 800 ° C. for 2 hours.
100 g of the calcined zinc-containing alumina support was impregnated with a solution prepared by dissolving ammonium paramolybdate and nickel nitrate in 100 g of water so that the amount of Mo was 9% by mass and that of Ni was 2% by mass in terms of oxides. The impregnated zinc-containing alumina support was heated and dried at 110 ° C. for 4 hours and calcined at 550 ° C. for 3 hours to prepare a hydrotreating catalyst A.
酸化亜鉛1を酸化亜鉛2に置き換えた以外は実施例1と同様にして、水素化処理触媒Bを調製した。 [Example 2] Preparation of hydrotreating catalyst B A hydrotreating catalyst B was prepared in the same manner as in Example 1 except that zinc oxide 1 was replaced with zinc oxide 2.
酸化亜鉛1を酸化亜鉛3に置き換えた以外は実施例1と同様にして、水素化処理触媒aを調製した。 [Comparative Example 1] Preparation of hydrotreating catalyst a A hydrotreating catalyst a was prepared in the same manner as in Example 1 except that zinc oxide 1 was replaced with zinc oxide 3.
酸化亜鉛1を酸化亜鉛4に置き換えた以外は実施例1と同様にして、水素化処理触媒bを調製した。 [Comparative Example 2] Preparation of hydrotreating catalyst b A hydrotreating catalyst b was prepared in the same manner as in Example 1 except that zinc oxide 1 was replaced with zinc oxide 4.
実施例1、2及び比較例1、2で調製した水素化処理触媒A、B、a、及びbの性状[Mo及びNiの担持量(触媒基準、酸化物換算)、亜鉛の担持量(担体基準、酸化物換算)、平均細孔径、及び比表面積]を表2に示す。表2中、「活性金属 活性金属量(質量%)」欄中の「Ni/Mo(上段) 2/9(下段)」は、当該触媒が触媒基準、酸化物換算で、Niを2質量%、Moを9質量%含有していることを意味する。なお、触媒の物理性状及び化学性状は、次の要領で測定した。 <Physical and chemical properties of the catalyst>
Properties of hydrotreating catalysts A, B, a and b prepared in Examples 1 and 2 and Comparative Examples 1 and 2 [Mo and Ni loading (catalyst standard, oxide conversion), zinc loading (support) Standard, oxide equivalent), average pore diameter, and specific surface area] are shown in Table 2. In Table 2, “Ni / Mo (upper stage) 2/9 (lower stage)” in the “active metal amount (mass%)” column indicates that the catalyst is based on catalyst and converted to oxide, and 2 mass% of Ni. This means that 9% by mass of Mo is contained. The physical properties and chemical properties of the catalyst were measured as follows.
a)測定方法及び使用機器:
・比表面積は、窒素吸着によるBET法により測定した。窒素吸着装置は、日本ベル(株)製の表面積測定装置(ベルソープMini)を使用した。
・平均細孔径は、水銀圧入法により測定した。水銀圧入装置は、ポロシメーター(MICROMERITICS AUTO-PORE 9200:島津製作所製)を使用した。 [1] Analysis of physical properties (specific surface area and average pore diameter)
a) Measuring method and equipment used:
The specific surface area was measured by the BET method using nitrogen adsorption. As the nitrogen adsorption device, a surface area measuring device (Bell Soap Mini) manufactured by Nippon Bell Co., Ltd. was used.
-The average pore diameter was measured by the mercury intrusion method. As the mercury intrusion apparatus, a porosimeter (MICROMERITICS AUTO-PORE 9200: manufactured by Shimadzu Corporation) was used.
・水銀圧入法は、毛細管現象の法則に基づく。水銀と円筒細孔の場合には、この法則は次式で表される。式中、Dは細孔径、Pは掛けた圧力、γは表面張力、θは接触角である。掛けた圧力Pの関数としての細孔への進入水銀体積を測定する。なお、触媒の細孔水銀の表面張力は484dyne/cmとし、接触角は130度とした。
式: D=-(1/P)4γcosθ b) Measurement principle:
・ The mercury intrusion method is based on the capillary phenomenon law. In the case of mercury and cylindrical pores, this law is expressed as: In the formula, D is the pore diameter, P is the applied pressure, γ is the surface tension, and θ is the contact angle. Measure the volume of mercury entering the pores as a function of the applied pressure P. The surface tension of the pore mercury of the catalyst was 484 dyne / cm, and the contact angle was 130 degrees.
Formula: D = − (1 / P) 4γcos θ
1)真空加熱脱気装置の電源を入れ、温度400℃、真空度5×10-2Torr以下になることを確認した。
2)サンプルビュレットを空のまま真空加熱脱気装置に掛けた。
3)真空度が5×10-2Torr以下となったら、当該サンプルビュレットを、そのコックを閉じて真空加熱脱気装置から取り外し、冷却後、重量を測定した。
4)当該サンプルビュレットに試料(触媒)を入れた。
5)試料入りサンプルビュレットを真空加熱脱気装置に掛け、真空度が5×10-2Torr以下になってから1時間以上保持した。
6)試料入りサンプルビュレットを真空加熱脱気装置から取り外し、冷却後、重量を測定し、試料重量を求めた。
7)AUTO-PORE 9200用セルに試料を入れた。
8)AUTO-PORE 9200により測定した。 c) Measurement procedure:
1) The vacuum heating deaerator was turned on, and it was confirmed that the temperature was 400 ° C. and the degree of vacuum was 5 × 10 −2 Torr or less.
2) The sample burette was emptied and placed on a vacuum heating deaerator.
3) When the degree of vacuum was 5 × 10 −2 Torr or less, the sample burette was removed from the vacuum heating and degassing device with its cock closed, and after cooling, the weight was measured.
4) A sample (catalyst) was placed in the sample bullet.
5) The sample burette containing the sample was placed in a vacuum heating and degassing apparatus, and held for 1 hour or more after the degree of vacuum became 5 × 10 −2 Torr or less.
6) The sample burette containing the sample was removed from the vacuum heating and degassing device, and after cooling, the weight was measured to obtain the sample weight.
7) The sample was put into the cell for AUTO-PORE 9200.
8) Measured with AUTO-PORE 9200.
a)分析方法及び使用機器:
・触媒中の金属分析は、誘導結合プラズマ発光分析(ICPS-2000:島津製作所製)を用いて行った。
・金属の定量は、絶対検量線法にて行った。 [2] Analysis of chemical composition a) Analysis method and equipment used:
The metal in the catalyst was analyzed using inductively coupled plasma emission spectrometry (ICPS-2000: manufactured by Shimadzu Corporation).
・ Quantitative determination of metals was performed by the absolute calibration curve method.
1)ユニシールに、触媒0.05g、塩酸(50質量%)1mL、フッ酸一滴、及び純水1mLを投入し、加熱して溶解させた。
2)溶解後、得られた溶液をポリプロピレン製メスフラスコ(50mL容)に移し換え、純水を加えて、50mLに秤量した。
3)当該溶液をICPS-2000により測定した。 b) Measurement procedure:
1) 0.05 g of catalyst, 1 mL of hydrochloric acid (50 mass%), one drop of hydrofluoric acid, and 1 mL of pure water were added to Uniseal, and dissolved by heating.
2) After dissolution, the resulting solution was transferred to a polypropylene volumetric flask (50 mL capacity), pure water was added, and weighed to 50 mL.
3) The solution was measured by ICPS-2000.
以下の要領にて、下記性状の減圧蒸留残渣油(VR)の水素化処理を行った。水素化処理触媒として、実施例1、2、比較例1、2で製造した触媒A、B、a、及びbをそれぞれ用いた。 <Hydrotreating reaction of heavy hydrocarbon oil>
In the following manner, a hydrogenation treatment of a vacuum distillation residue oil (VR) having the following properties was performed. Catalysts A, B, a, and b produced in Examples 1 and 2 and Comparative Examples 1 and 2 were used as hydrotreating catalysts, respectively.
1)60℃に加温した試料を三角フラスコに25g採取し、エアーコンデンサーを取り付けて100℃の油浴に挿入し、24時間保持した。
2)当該試料を充分に振とうした後、10.5gをガラスビーカーにサンプリングした。
3)試料の入ったガラスビーカーを、100℃で10分間加温した。
4)乾燥したガラス繊維濾紙(直径47mm、気孔径1.6μm)を3枚重ねでセットし、減圧ポンプで80kPaまで減圧した減圧濾過器に、前記試料を投入し、30秒後に40kPaまで減圧した。
5)濾過が完了し、濾紙表面が乾いた後に、さらに5分間減圧を続けた。
6)減圧ポンプ停止後、濾過器をアスピレータで引きながら25mLの洗浄溶剤(ヘプタン85mL+トルエン15mL)で漏斗とフィルター全域を洗浄した。
7)さらに20mLヘプタンで当該濾紙を洗浄した後、最上部の濾紙(上から1枚目)を取り外して、下部の濾紙を20mLヘプタンで洗浄した。
8)上から1枚目及び2枚目の濾紙を、110℃で20分乾燥後、30分放冷した。
9)濾過前に対する濾過後の1枚目及び2枚目濾紙の各重量増加分を測定し、1枚目濾紙の増加重量から2枚目濾紙の増加重量を差し引いた重量を、試料採取重量に対する百分率としたものを、潜在セジメント(質量%)とした。
なお、濾過が25分間で終了しない場合はサンプル量を5gあるいは2gとして再測定した。 <Measurement procedure of potential sediment content>
1) 25 g of a sample heated to 60 ° C. was collected in an Erlenmeyer flask, an air condenser was attached, and the sample was inserted into a 100 ° C. oil bath and held for 24 hours.
2) After fully shaking the sample, 10.5 g was sampled into a glass beaker.
3) The glass beaker containing the sample was heated at 100 ° C. for 10 minutes.
4) Set three sheets of dried glass fiber filter paper (diameter 47 mm, pore diameter 1.6 μm), put the sample into a vacuum filter whose pressure was reduced to 80 kPa with a vacuum pump, and reduced pressure to 40 kPa after 30 seconds .
5) After filtration was completed and the surface of the filter paper was dried, the pressure reduction was continued for another 5 minutes.
6) After stopping the vacuum pump, the funnel and the entire filter area were washed with 25 mL of a washing solvent (85 mL of heptane + 15 mL of toluene) while pulling the filter with an aspirator.
7) After the filter paper was further washed with 20 mL heptane, the uppermost filter paper (first sheet from the top) was removed, and the lower filter paper was washed with 20 mL heptane.
8) The first and second filter papers from the top were dried at 110 ° C. for 20 minutes and then allowed to cool for 30 minutes.
9) Measure the respective weight increments of the first and second filter papers after filtration relative to the pre-filtration, and subtract the additional weight of the second filter paper from the increased weight of the first filter paper to the sampling weight The percentage was defined as the latent segment (mass%).
In addition, when filtration did not complete | finish in 25 minutes, the sample amount was measured again as 5 g or 2 g.
アスファルテン分は、試料にトルエンを加えた後、セルロースフィルターで濾過し、トルエン不溶解分を回収した。この不溶性分をアスファルテン分とした。
レジン分は、試料にトルエンを加えた後、セルロースフィルターで濾過し、濾液であるトルエン溶解分を濃縮した。この濃縮物にヘプタンを加えたヘプタン溶液を活性アルミナ充填カラムに流通させ、飽和、芳香族、レジン分に分離し、レジン分を回収した。 The contents of nickel and vanadium were in accordance with the Japan Petroleum Institute Standard JPI-5S-62-2000 “Petroleum Products Metal Analysis Test Method (ICP Luminescence Analysis Method)”.
The asphaltene content was filtered through a cellulose filter after toluene was added to the sample, and the toluene-insoluble content was recovered. This insoluble content was defined as asphaltene content.
Toluene was added to the sample, and the resin was filtered through a cellulose filter, and the toluene-soluble component as a filtrate was concentrated. A heptane solution obtained by adding heptane to this concentrate was passed through an activated alumina packed column and separated into saturated, aromatic and resin components, and the resin component was recovered.
触媒の予備硫化は、減圧軽油により、水素分圧10.3MPa、370℃において12時間行った。その後、活性評価用の原料油に切り替えた。 Catalyst pretreatment conditions:
The preliminary sulfidation of the catalyst was carried out with a vacuum gas oil at a hydrogen partial pressure of 10.3 MPa and 370 ° C. for 12 hours. Then, it switched to the raw material oil for activity evaluation.
反応温度;385℃、
圧力(水素分圧);10.3MPa、
液空間速度 ;0.4h-1、
水素/油比 ;1690m3/m3。 Reaction conditions:
Reaction temperature: 385 ° C.
Pressure (hydrogen partial pressure); 10.3 MPa,
Liquid space velocity; 0.4 h −1 ,
Hydrogen / oil ratio: 1690 m 3 / m 3 .
油種;中東系原油の減圧蒸留残渣油、
密度(15℃);1.037g/cm3、
硫黄成分;4.27質量%、
バナジウム;91ppm、
ニッケル;54ppm、
アスファルテン分;7.8質量%。 Raw oil properties:
Oil type: Vacuum distillation residue of Middle Eastern crude oil,
Density (15 ° C.); 1.037 g / cm 3 ;
Sulfur component; 4.27% by mass;
Vanadium; 91 ppm,
Nickel; 54 ppm,
Asphaltene content: 7.8% by mass.
〔1〕脱硫率(HDS)(%):原料油中の硫黄分を脱硫反応によって硫化水素に転換することにより、原料油から消失した硫黄分の割合を脱硫率と定義し、原料油及び生成油の硫黄分析値から以下の式(1)により算出した。
〔2〕脱硫反応速度定数(Ks):生成油の硫黄分(Sp)の減少量に対して、2次の反応次数を得る反応速度式の定数を脱硫反応速度定数(Ks)とする。以下の式(2)により算出した。なお、反応速度定数が高い程、触媒活性が優れていることを示している。
〔3〕脱硫比活性(%):触媒Aの脱硫反応速度定数を100としたときの相対値で示した。以下の式(3)により算出した。
〔4〕脱金属率(HDM)(%):原料油から消失した金属分(ニッケルとバナジウムの合計)の割合を脱金属率と定義し、原料油及び生成油の金属分析値から以下の式(4)により算出した。 The catalytic activity was analyzed by the following method. The reactor was operated at 385 ° C., and the product oil 20 days after the start of operation was collected and its properties (desulfurization rate (HDS) (%), desulfurization reaction rate constant (Ks), desulfurization specific activity (%), demetalization rate, (HDM)) was analyzed. The results are shown in Table 3.
[1] Desulfurization rate (HDS) (%): By converting the sulfur content in the feedstock to hydrogen sulfide by desulfurization reaction, the proportion of sulfur lost from the feedstock is defined as the desulfurization rate. It calculated by the following formula | equation (1) from the sulfur analysis value of oil.
[2] Desulfurization reaction rate constant (Ks): The desulfurization reaction rate constant (Ks) is a constant in the reaction rate equation for obtaining the second order reaction order with respect to the reduction amount of the sulfur content (Sp) of the product oil. It calculated by the following formula | equation (2). The higher the reaction rate constant, the better the catalytic activity.
[3] Desulfurization specific activity (%): indicated as a relative value when the desulfurization reaction rate constant of the catalyst A is 100. It calculated by the following formula | equation (3).
[4] Demetallation rate (HDM) (%): The ratio of metal components (total of nickel and vanadium) disappeared from the feedstock oil is defined as the demetallation rate. Calculated according to (4).
脱硫反応速度定数=〔1/Sp-1/Sf〕×(LHSV) ………(2)
式中、Sf:原料油中の硫黄分(質量%)、
Sp:生成油中の硫黄分(質量%)、
LHSV:液空間速度(h-1)。
脱硫比活性(%)=(各触媒の脱硫反応速度定数/触媒Aの脱硫反応速度定数)×100………(3)
脱金属率(%)=〔(Mf-Mp)/Mf〕×100 ………(4)
式中、Mf:原料油中のニッケルとバナジウムの合計(質量ppm)、
Mp:生成油中のニッケルとバナジウムの合計(質量ppm)。 Desulfurization rate (%) = [(Sf−Sp) / Sf] × 100 (1)
Desulfurization reaction rate constant = [1 / Sp-1 / Sf] × (LHSV) (2)
In the formula, Sf: sulfur content (mass%) in the raw material oil,
Sp: Sulfur content (% by mass) in the product oil,
LHSV: Liquid space velocity (h -1 ).
Desulfurization specific activity (%) = (desulfurization reaction rate constant of each catalyst / desulfurization reaction rate constant of catalyst A) × 100 (3)
Metal removal rate (%) = [(Mf−Mp) / Mf] × 100 (4)
In the formula, Mf: total of nickel and vanadium in the feedstock (mass ppm),
Mp: Sum of nickel and vanadium in the produced oil (mass ppm).
前記の水素化処理反応で得た運転日数20日目の生成油から求めた脱硫比活性、脱金属率、レジン分、アスファルテン分、レジン分に対するアスファルテン分の含量比(質量比、[アスファルテン分(質量%)]/[レジン分(質量%)])、及び潜在セジメント含量の結果を表3に示す。 [Analysis of product oil]
Desulfurization specific activity, demetalization rate, resin content, asphaltene content, content ratio of asphaltene content to resin content (mass ratio, [asphaltene content ( Mass%)] / [resin content (mass%)]) and the latent sediment content results are shown in Table 3.
これらの結果から、特定の物性を有する酸化亜鉛粒子を含有する担体を用いた水素化処理触媒を用いることにより、水素化処理触媒の脱硫活性を低下させることなく、水素化処理した重質炭化水素油中の潜在セジメントの含有量を低くでき、貯蔵安定性を高められることが明らかである。 As a result, all the catalysts had almost the same desulfurization activity and demetallation rate. On the other hand, regarding the resin content and the amount of potential sediment in the product oil, the amount of resin is larger when the catalyst A or the catalyst B is used than when the catalyst a or the catalyst b is used. There were obviously few. That is, the product oil obtained by using the catalyst A or the catalyst B was less likely to generate sediment than the oil obtained by using the catalyst a or the catalyst b, and was excellent in storage stability.
From these results, heavy hydrocarbons hydrotreated without reducing the desulfurization activity of the hydrotreating catalyst by using a hydrotreating catalyst using a support containing zinc oxide particles having specific physical properties. It is clear that the content of latent sediment in the oil can be lowered and the storage stability can be improved.
Claims (2)
- 平均粒子径が2~12μmの酸化亜鉛粒子を担体基準で1~15質量%含有する亜鉛含有アルミナ担体に、少なくとも1種の周期表第6族金属が担持されており、平均細孔径が18~35nmであり、比表面積が70~150m2/gであることを特徴とする、重質炭化水素油の水素化処理触媒。 At least one Group 6 metal of the periodic table is supported on a zinc-containing alumina support containing 1 to 15% by mass of zinc oxide particles having an average particle diameter of 2 to 12 μm based on the support, and an average pore diameter of 18 to A heavy hydrocarbon oil hydrotreating catalyst characterized by having a specific surface area of 35 to 35 nm and 70 to 150 m 2 / g.
- 請求項1記載の水素化処理触媒の存在下、温度300~420℃、圧力3~20MPa、水素/油比400~3000m3/m3、及び液空間速度0.1~3h-1の条件で、重質炭化水素油の接触反応を行うことを特徴とする重質炭化水素油の水素化処理方法。 2. In the presence of the hydrotreating catalyst according to claim 1, under conditions of a temperature of 300 to 420 ° C., a pressure of 3 to 20 MPa, a hydrogen / oil ratio of 400 to 3000 m 3 / m 3 , and a liquid space velocity of 0.1 to 3 h −1 . A method for hydrotreating heavy hydrocarbon oil, characterized by carrying out a catalytic reaction of the heavy hydrocarbon oil.
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